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JOURNAL OF APPLIED POLYMER SCIENCE VOL. 19, PP. 2167-2177 (1975)
An Empirical Model Relating the Molecular Weight
Distribution of High-Density Polyethylene to the
Shear Dependence of the Steady Shear Melt Viscosity
B. H. BERSTED, Research and Development Department, Amoco
Chemicals Corporation,Amoco Research Center, Naperville, Illinois 60540
Synopsis
An empirical model has been developed to relate molecular weight distribution to the shear
dependence of the steady shear viscosity in high-density polyethylene melts. It uses a molecular
weight, M,,which partitions molecular weights into two classes;those below M,contribute to the
viscosity as they do at zero shear, and those above M,contribute to the viscosity as though they
were of molecular weight M,at zero shear. Each individual molecular weight species contributes
on the basis of its weight fraction. M, is proposed to be a unique function of the shear rate.
Using this method of treating the molecular weight distribution, and the zero shear relation for
relating 90 to molecular weight, the calculated steady shear viscosities a t various shear rates for
polyethylene samples of widely varying polydispersities agree well with experimental results.
The model makes no judgment on the existence or importance of entanglements in non-Newto-
nian behavior since it has no specificparameters involving an entanglement concept. Use of the
model suggests that for the samples studied, only the upper portion of the molecular weight dis-
tribution contributes toward the experimentally observed decrease of steady shear viscosity with
shear rate for shear rates of up to 10,OOO sec-l. The lower molecular weight species are assumed
to behave in a Newtonian manner.
INTRODUCTION
Numerous theories14 have been advanced to account for the shear depen-
dence of the v
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